CN103975090A - Diffusion blocking layer in an exhaust treatment unit - Google Patents
Diffusion blocking layer in an exhaust treatment unit Download PDFInfo
- Publication number
- CN103975090A CN103975090A CN201280059088.3A CN201280059088A CN103975090A CN 103975090 A CN103975090 A CN 103975090A CN 201280059088 A CN201280059088 A CN 201280059088A CN 103975090 A CN103975090 A CN 103975090A
- Authority
- CN
- China
- Prior art keywords
- metal
- upper layer
- oxide
- metal sheet
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000009792 diffusion process Methods 0.000 title claims abstract description 53
- 230000000903 blocking effect Effects 0.000 title abstract 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 123
- 239000002184 metal Substances 0.000 claims abstract description 123
- 238000000034 method Methods 0.000 claims abstract description 71
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011651 chromium Substances 0.000 claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 33
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010941 cobalt Substances 0.000 claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 28
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 27
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 57
- 150000004706 metal oxides Chemical class 0.000 claims description 56
- 239000004411 aluminium Substances 0.000 claims description 31
- 239000007858 starting material Substances 0.000 claims description 27
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 21
- 238000005219 brazing Methods 0.000 claims description 16
- 238000005476 soldering Methods 0.000 claims description 16
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 15
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 14
- 238000007669 thermal treatment Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 167
- 239000002344 surface layer Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 31
- 241000264877 Hippospongia communis Species 0.000 description 29
- 239000002912 waste gas Substances 0.000 description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910003470 tongbaite Inorganic materials 0.000 description 9
- 230000002349 favourable effect Effects 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 4
- 150000001869 cobalt compounds Chemical class 0.000 description 4
- 150000002816 nickel compounds Chemical class 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- -1 Qi Zhongge Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2422—Mounting of the body within a housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
- C23C8/14—Oxidising of ferrous surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2450/00—Methods or apparatus for fitting, inserting or repairing different elements
- F01N2450/22—Methods or apparatus for fitting, inserting or repairing different elements by welding or brazing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2807—Metal other than sintered metal
- F01N3/281—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Geometry (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Heat Treatment Of Articles (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a method for generating a diffusion blocking layer (1), comprising aluminum oxide (8) on a metal plate (2), which consists of a base material (3), which comprises at least iron (Fe), chromium (Cr) and aluminum (Al). The invention further relates to integrating said method into the production of an exhaust treatment unit (12), wherein the exhaust treatment unit (12) has a honeycomb body (13) and a housing (14) and at least the honeycomb body (13) or the housing (14) is formed with a metal plate (2) and the metal plate (2) consists of a base material (3) which comprises at least iron (Fe), chromium (Cr) and aluminum (Al). The metal plate (2) thus comprises, at least in a sub-region (5), a surface layer (7) which comprises at least aluminum oxide (8) and a metal (9) from the group consisting of cobalt (Co) and nickel (Ni).
Description
The present invention relates to prepare the method for diffusion impervious layer on metal sheet, and the method for process gas treatment unit and emission-control equipment.The present invention be more particularly directed to the technical field for the waste gas technology of motor vehicle, metal sheet or emission-control equipment can be used in the waste gas system of motor vehicle.
Motor vehicle and commercial car are subject to the waste gas system of many waste gas prescribed limits and suitable constructions and have guaranteed to meet these restrictions.The waste gas system with at least one emission-control equipment being formed by metallic honeycomb bodies is at least partly known.This metallic honeycomb bodies is for example used as the carrier of catalytically active material, for storing the carrier of coating and/or the carrier of solids precipitation device of waste gas component.For this reason, emission-control equipment is conventionally coated to affect the various components of the waste gas on different positions in the waste gas system of motor vehicle or to make described various component reaction or other function of performance off gas treatment at least in part.
In at least part of metallic honeycomb bodies of emission-control equipment, because soldering processes produce brazed joint, therefore each assembly of metallic honeycomb bodies be fixed on each other and/or this with it, and/or realize honeycomb and be arranged in for a long time shell.
This metalloid honeycomb and shell are formed by the base mateiral with following performance especially:
the tinsel of honeycomb
Microstructure: ferrite
Composition: the FeCrAl alloy with the chromium content of at least 12 % by weight and the aluminium content of at least 2.5 % by weight.Can add rare earth element, Y and/or Hf to control Al
2o
3the formation of upper layer.
Examples of materials: German steel classification No.1.4767 or 1.4725 materials
Material thickness: 20 μ m[microns] to 150 μ m
Form: structurizing at least in part; Smooth
shell
Microstructure: austenite or ferrite
Material thickness: 0.1mm[millimeter] to 3mm
Form: cylindrical; Oval; Taper
braze material
Form: brazing powder; Soldering bar
Composition: nickel-based brazing material, Qi Zhongge, phosphorus and silicon exist as main additive.Very particularly preferably the ratio of main additive reduces in the following order: chromium, phosphorus, silicon.The chromium content of nickel-based brazing material for example, preferably higher than the chromium ratio in honeycomb material, within the scope of 23-25 % by weight.Main additive phosphorus and silicon should be no more than the ratio of chromium altogether.
Examples of materials: this class nickel-based brazing material can for example be obtained by WallColmonoy Ltd. with title Nicrobraz.
In the manufacture of emission-control equipment, may provide brazed joint by the only specific point of contact between the assembly of emission-control equipment necessary or that clearly wish.Due to the brazed joint of these (only) local restricted in honeycomb and/or between honeycomb and shell, the handiness of emission-control equipment is kept.This handiness causes emission-control equipment can realize higher longterm strength in the time of the waste line for motor vehicle, although temperature and pressure prevailing changes in waste gas system.The brazed joint of wishing can be for example by the braze material specific point of contact that only (target) is introduced into honeycomb or emission-control equipment is produced.In this article, also passivation layer can be applied in the prospective region of emission-control equipment, thereby prevent undesirable joint on point of contact.To consider that undesirable braze material flows and/or undesirable alloying element is spread by base mateiral herein.
Although having proposed some measures forms brazed joint and/or avoids undesirable other compound (secondary joint hereinafter on point of contact with target in the manufacture at this class emission-control equipment connecting by high temperature brazing under vacuum or shielding gas; diffusion joint); still need to simplify for mass-produced the method; make it safer, carry out more cheaply and/or avoid other interference effect to soldering processes.
Therefore, the object of the invention is to solve at least in part those technical problems to described in prior art.Especially, should provide the method for preparing diffusion impervious layer on metal sheet, it is allowed especially accurately and positioningly on metal sheet, forms brazed joint and reduce the risk that forms subsequently undesirable diffusion joint.In addition, should propose to manufacture the method for emission-control equipment, make on the predetermined position of brazed joint (only) on emission-control equipment to produce and to avoid undesirable diffusion joint in emission-control equipment.In addition, should describe emission-control equipment, wherein brazed joint (only) produces and can avoid undesirable diffusion joint on other point of contact on predetermined point of contact.
These objects are by prepare the method for diffusion impervious layer on the metal sheet of feature with claim 1, and the method for manufacture emission-control equipment and the emission-control equipment of feature by having claim 11 of the feature by having claim 9 are realized.Other favourable embodiment of the present invention is described in dependent claims.Each feature described in claim can and can be supplemented by the illustrative contents from specification sheets with any technical significant mode combination with one another, obtains other embodiment of the present invention.Especially, relate on metal sheet, prepare diffusion impervious layer method, manufacturing the method for emission-control equipment and the feature of emission-control equipment can combination with one another or be applied to corresponding other theme of the present invention.
On metal sheet, prepare the method for wrapping salic diffusion impervious layer and there are at least following steps, wherein metal sheet is by comprising at least iron (Fe, ordination number 26), the base mateiral composition of chromium (Cr, ordination number 24) and aluminium (Al, ordination number 13):
A) provide metal sheet,
B) at least one is selected to cobalt/cobalt oxide (particularly Co
3o
4itself until 900 DEG C be all stable) and the metal oxide of nickel oxide (particularly NiO) or at least one can be formed because temperature improves at least one subarea that at least one starting compound that is selected from cobalt/cobalt oxide and nickel oxide is applied over metal sheet surface as upper layer
C) under vacuum or shielding gas, have on the metal sheet of described upper layer and carrying out more than 650 DEG C thermal treatment, making only on described at least one subarea of upper layer, to form the salic diffusion impervious layer of bag.In this case, (mainly) changes into aluminum oxide and produces aluminum oxide because metal oxide is reduced into alumina that metal and (simultaneously) diffuse out from base mateiral.
Metal sheet particularly thickness is 10 μ m[microns] to 3mm[millimeter] tinsel.In the time that metal sheet is used as the tinsel in honeycomb, the thickness of metal sheet is very particularly preferably 30-120 μ m; On the other hand, in the time that metal sheet is used as shell, thickness is for example 0.5-2.2mm.Metal sheet also can have structure (such as ripple, projection, embossing etc.) and/or perforate.Metal sheet is optionally formed by (type such as non-woven, braiding, woven fabrics) fine wire, has separately the length in diameter and 30 μ m to the 10mm scopes within the scope of 5-100 μ m.
The step of the method is b) special by dip-coating method or deposition method or carry out for other appropriate method that deposits or apply.At least one is selected to cobalt/cobalt oxide (Co herein,
3o
4) and the metal oxide of nickel oxide (particularly NiO) and/or at least one can this quasi-metal oxides of thermosetting starting compound be applied at least one subarea of metal sheet surface as upper layer.Preferably accurately single type metal oxide is applied on predetermined metal plate.The subarea on described surface can relate to (single) section or multiple/many (relatively little) section continuously on surface.In addition, subarea can only relate to a side of metal sheet surface.Very particularly preferably metal sheet at least 90% or even all surfaces selected metal oxide and/or starting compound are provided.Step b) after, between metal oxide and/or starting compound and base mateiral, there is especially firm material key.Especially, for example apply in b) in the step of method due to independent (previous) thermal treatment and/or because the thermal treatment of step in c) forms the starting compound of cobalt/cobalt oxide and/or nickel oxide.The example of this class starting compound is the oxyhydroxide of nickel and/or cobalt.Therefore this starting compound also can be described as metal oxide forming agent or metal oxide precursor type.It is special herein that what wish is that this conversion of metal oxide or form is also carried out under vacuum and/or shielding gas.
Step c) in, heat-treat.Herein, particularly first starting compound dissolves at least partly and/or decomposes because temperature improves, and therefore exists now at least one to be selected from the metal oxide of nickel oxide and cobalt/cobalt oxide.
Especially, the thermal treatment of step in c) can easily adjust to be suitable for forming of material by those skilled in the art, particularly aspect the selection of suitable temp.The heat treated temperature of capable of regulating or time length, the shorter thermal treatment of temperature tolerable for example raising.Due to the heating of metal sheet, the aluminium being present in base mateiral spreads and infiltrates wherein to the direction of upper layer.In upper layer, aluminium reacts to form aluminum oxide with the oxygen that is incorporated into metal oxide especially.Especially, this reaction is carried out according to following reaction equation:
3Co
3O
4+8Al=＞9Co+4Al
2O
3
Or
3NiO+2Al=＞3Ni+Al
2O
3
Especially, first therefore aluminum oxide form in the surf zone of metal sheet, because the aluminium being diffused in upper layer reacts with the oxygen that is present in the metal oxide in upper layer herein.Therefore, on the surface of metal sheet, (only) forms the diffusion impervious layer being made up of aluminum oxide in upper layer especially, its at least greatly (completely) prevented that other Elements Diffusion is in upper layer, particularly other element in base mateiral.Especially, further same (completely) prevented that element (for example, from upper layer) is diffused into base mateiral.
After carrying out the thermal treatment of step in c), in upper layer, there is diffusion impervious layer, particularly wrap salic diffusion impervious layer.In addition, especially, find to be selected from there the metal element of cobalt and nickel.Therefore, especially, the step of carrying out the method c) after, be particularly suitable for forming subsequently the matallic surface layer of brazed joint.
Metal oxide in upper layer and/or starting compound are particularly useful as the carrier of oxygen, make (from base mateiral) aluminium (only) react to form aluminum oxide with the oxygen providing like this.
The thermal treatment of step in c) is carried out especially under vacuum or under shielding gas atmosphere.Especially, do not introduce oxygen.The reaction that aluminum oxide forms that causes in the presence of oxygen of during Heat Treatment only even occurred under the oxygen of (being therefore present in upper layer) of the metal oxide in (at least) upper layer and/or the combination of starting compound institute existence especially before thermal treatment.
Although vacuum or shielding gas atmosphere, still can there is a small amount of oxygen in during Heat Treatment.But this " residual oxygen " is not enough to form the non-perviousness structure of diffusion of alumina layer on the surface of metal sheet.
Those skilled in the art are familiar with these alloyings or method of converting, make technician easily can understand, imitate and control chemical process described herein.In addition, provide illustrative example below.
As the example of suitable heat treatment, can be chosen in vacuum atmosphere 1000 DEG C of above envrionment temperatures and the treatment time of 10-60 minute.Very particularly preferably be no more than the envrionment temperature of 1200 DEG C.Can point out that thermal treatment also can carry out in multiple stages herein, therefore for example can the envrionment temperature below 1000 DEG C under, under optional more than 400 DEG C or even more than 800 DEG C envrionment temperature, carry out the pre-heating stage of 20-60 minute.Equally, after this, can be cooling stages, for example continue 15-40 minute.Thermal treatment can amount to and continue at least 2 hours especially, optionally even at least 3 hours.
In the preferred embodiment of the method, metal oxide and/or starting compound are present in the upper layer of step in b) with the ratio of at least 40 % by weight.Metal oxide and/or starting compound preferably with the ratio of at least 60 % by weight, particularly preferably exist with the ratio of at least 80 % by weight herein.Especially, upper layer does not comprise any iron (Fe) and/or does not comprise any chromium (Cr).Preferred surface layer does not comprise any aluminium (Al).
In a favourable embodiment, the step of carrying out the method c) after, aluminum oxide is uniformly distributed in upper layer.In this article, " evenly " means especially aluminum oxide (on thickness) and is distributed in equably in upper layer, and particularly deviation is no more than 5 % by weight.Deviation can be measured by contrasting the ratio of measuring with % by weight in each measured zone especially.In every kind of situation of these measured zone particularly including 50-400nm
2, particularly 100nm
2the area of [square nanometers], but be never limited to this area size.
In another favourable embodiment, carry out step c) after, the ratio that is present in the metal of metal oxide in upper layer and/or starting compound with element form improves at least 5 % by weight, preferably at least 10 % by weight, particularly preferably at least 20 % by weight.Especially, this ratio of the metal existing with element form now improves (mainly) and results from reacting of aluminium and metal oxide and/or starting compound.Therefore the aluminium being diffused into upper layer from base mateiral obtain oxygen from metal oxide and/or starting compound, therefore forming element metal in upper layer.Especially, be present at least 80 % by weight metal oxides in upper layer and/or starting compound before c) in step and c) change into metal element owing to carrying out step.Preferably at least 90 % by weight, very particularly preferably at least 99 % by weight transform.
In another favourable embodiment, al proportion in base mateiral in the method step in a) is 1-7 % by weight, and especially, the al proportion in the upper layer in the method step in b) is no more than 2 % by weight, preferably be no more than 1 % by weight, be particularly preferably no more than 0.1 % by weight.
In a favourable embodiment, carry out step c) al proportion in later diffusion impervious layer be at least 15 % by weight, preferably at least 20 % by weight.
Diffusion impervious layer forms especially or extends from region between upper layer and base mateiral in the region of upper layer, and it just has at least 15 % by weight, the preferably al proportion of at least 20 % by weight in step after c).
Especially, preferably in whole upper layer, form suitable diffusion impervious layer, that is, especially, just carry out step c) after, the al proportion in whole upper layer is at least 15 % by weight, preferably at least 20 % by weight.
Especially, according to step c) heat-treat method after, aluminium to be to exceed at least 2 times of the % by weight ratios of the aluminium in (always) base mateiral that is present in metal sheet, and preferably the % by weight ratio of at least 3 times is present in the whole region of upper layer and is at least 5 % by weight.
In a favourable embodiment, carry out step b) after, upper layer have be no more than 1 μ m[micron] thickness, be particularly no more than 0.5 μ m, be preferably no more than 0.25 μ m, be particularly preferably no more than the thickness of 0.1 μ m.
Especially, the thickness of upper layer and heat treated intensity (temperature and time length) affect the formation of diffusion impervious layer in upper layer.Especially, providing of thin especially upper layer causes diffusion impervious layer adequate relief to be formed in whole upper layer.
The formation of diffusion impervious layer causes having prevented from the Elements Diffusion beyond the aluminium of base mateiral especially in upper layer.Especially, diffusion impervious layer (greatly) has prevented that other Elements Diffusion is in base mateiral.
Especially, relatively thick upper layer and/or not too strong thermal treatment cause forming aluminum oxide near (only or mainly) metal sheet surface in upper layer, are wherein started to form the corresponding multilayered structure of following order by base mateiral: base mateiral, diffusion impervious layer (having the metal element of metal oxide), metal oxide and/or starting compound.Especially, aluminium does not diffuse into (on thickness direction) in whole surface, make metal oxide only Partial Conversion become metal element.
In the favourable embodiment of the method, the base mateiral of step in a) has step metal oxide b) and/or the metal of starting compound that are no more than 20 % by weight.Especially, the base mateiral of step in a) comprises and is no more than 10 % by weight, is preferably no more than 5 % by weight, is particularly preferably no more than step metal oxide b) and/or the metal of starting compound of 1 % by weight.Especially, the base mateiral of step in a) comprises 0 % by weight step metal oxide b) and/or the metal of starting compound.
Especially, in upper layer the metal ratio of metal oxide not because the metal from base mateiral improves because the thermal treatment of step in c) is diffused in upper layer.The raising (only) of metal ratio is reduced into metal element by metal oxide, and the aluminum oxidation being simultaneously diffused in upper layer forms aluminum oxide and occurs.
In addition, propose to manufacture the method for emission-control equipment, wherein emission-control equipment has honeycomb and shell and at least honeycomb or shell metal sheet form.Especially, above those about described in metal sheet are applicable to the method proposing similarly herein.Metal sheet forms by comprising at least base mateiral of iron (Fe), chromium (Cr) and aluminium (Al).
The method comprises at least following steps:
I) provide at least one metal sheet to form shell or honeycomb,
Ii) at least one be selected to the metal oxide of cobalt/cobalt oxide and nickel oxide or at least one can be formed because temperature improves at least one surperficial subarea that at least one starting compound that is selected from the metal oxide of cobalt/cobalt oxide and nickel oxide is applied over described at least one metal sheet as upper layer
Iii) form honeycomb and honeycomb inserted in shell,
Iv) braze material is put at least on honeycomb or shell at least one brazing area,
V) more than 1000 DEG C, under vacuum or shielding gas, comprising on described at least one metal sheet of metal oxide and carrying out soldering processes, making:
-only form the salic diffusion impervious layer of bag on described at least one subarea in upper layer, wherein metal oxide is reduced into metal and the alumina that diffuses out from base mateiral changes into aluminum oxide, and
-on described at least one metal sheet, at least one brazing area, form brazed joint.
Above about a) and the b) step I of described those methods that are specially adapted to propose of step herein) and ii).
The step I of the method proposing)-v) in succession carry out with the order proposing herein especially.But step I is v) especially at step I ii) before or carry out simultaneously.
Especially, the metal sheet herein proposing about emission-control equipment is refractory metal plate, and it is particularly suitable for withstanding for a long time the temperature variation in the waste gas system of motor vehicle and power requires and corrosive atmosphere.Herein, more than 800 DEG C temperature and/or the considerable pressure pulse by the combustion processes generation in the oil engine of motor vehicle can act on emission-control equipment.
About base mateiral, preferably use comprises chromium and the aluminium iron material as main alloy element in addition.Especially, chromium ratio is at least 3 times of al proportion.Very particularly preferably chromium ratio is for example 12-25 % by weight, and al proportion is for example 1-7 % by weight, preferably 2.5-6 % by weight.In addition, can use if beginning is to the base mateiral as described in tinsel and/or shell, by reference this description is incorporated to herein.
Upper layer is the subarea of (only) covered metal plate preferably, and it is arranging that metal sheet is to form point of contact with other assembly of emission-control equipment after forming emission-control equipment.Especially, upper layer only covers neither wishes that brazed joint do not wish the point of contact of diffusion joint yet, and therefore the combination of the emission-control equipment assembly that forms the point contacting with each other does not occur.But upper layer also can be applied on the subarea of metal sheet or the whole surface of metal sheet, therefore brazed joint can be arranged thereon subsequently.It is closed that upper layer itself should be, and, do not form especially the hole of the significant base mateiral through metal sheet that is.Especially, upper layer is not configured to catalyst layer, is particularly not used in the reaction of the pollutent in waste gas.
First upper layer causes no longer existing at point of contact place (as the main ingredient of the base mateiral of metal sheet) elemental chromium and iron.Known chromium and iron all have very high avidity to carbon, when have carbon under soldering condition time, chromium carbide inevitably occurs and form (iron-chromium carbide forms).On the other hand, cobalt and nickel do not form corresponding carbide.Cobalt and nickel can with chromium and the complete miscible of iron, but itself do not there is the catalysis that (significantly) can be used for off gas treatment here.
During soldering processes because local carbon availability forms the chromium carbide bridge (secondary joint, diffusion joint) of secure adhesion at other assembly of metal sheet and emission-control equipment or with the contact area of itself.Under hostile environment, form like this carbide skeleton of three-dimensional fine distribution.This carbide skeleton firmly connects metal sheet/is welded on other assembly of own and/or emission-control equipment, therefore affects the handiness that metal sheet is for example arranged in emission-control equipment, i.e. the handiness of emission-control equipment itself.Applying the upper layer that chromium and iron are separated interrupts thus or has suppressed the mechanism that chromium carbide forms.This will explain hereinafter.
Especially, in upper layer, provide metal oxide (especially only) to provide and produce oxygen high temperature resistant and that corrosion-resistant alumina layer is required.Therefore, protectiveness alumina layer can form during soldering processes (it carries out especially under shielding gas or vacuum, there is no oxygen) on metal sheet.Therefore, especially, saved another oxidizing process subsequently for emission-control equipment.Corresponding oxidation aluminium lamination produces by process emission-control equipment in oxygen-containing atmosphere at the temperature of at least 400 DEG C by this oxidizing process conventionally on emission-control equipment.
Especially, in upper layer, provide metal oxide to cause suitable alumina layer (only) during soldering processes to provide in the pre-stator region of metal sheet or emission-control equipment.In addition, in upper layer, metal oxide changes into metal element and produces the upper layer that obtains metallicity, has therefore kept the braze-ability in these regions of upper layer.Prevent from thus forming spinel by the metal oxide in upper layer especially, thereby advantageously kept the metallicity of upper layer.
Assembly to be brazed, for example tinsel and shell can have carbonaceous liquid as the resistates of ROLLING OIL or graining oil (corrugating oil).Due to wicking action, these liquid retreat to territory, fish tail bearing, for example territory, fish tail bearing between surge layer and the smooth layer of honeycomb, therefore wetting these assemblies.After introducing in brazing device, start to vacuumize or introduce shielding gas.Meanwhile, improve temperature.After reaching flash-point, because the shortage liquid of oxygen no longer may burn, therefore more than approximately 400 DEG C, start cracking process, and cause forming pure hyperergy carbon.This cracking process is also occurring during the manufacture of brazed joint under shielding gas, because oxygen is also replaced in this case, carbon containing is manufactured auxiliary agent by cracking.Carbon extracts chromium (the formation point of contact) abutment surface by the permanent coupling unit of carbide bridge from assembly, wherein forms chromium carbide or siderochrome carbide.Even if this carbide bridge forms under the conventional brazing temperature more than 1050 DEG C and also no longer can be disengaged.In addition, the alloy of the base mateiral of assembly has chromium deficiency now.
Form therein in the critical temperature range of approximately 400 to 800 DEG C of chromium carbide, aluminium is diffused in upper layer from base mateiral.Then the reactive metal oxide that is selected from cobalt/cobalt oxide and nickel oxide in aluminium and upper layer or on metal sheet surface.Form there aluminum oxide, and metal oxide reverts back metal element.In this region, the formation of alumina layer produces diffusion impervious layer, and therefore alloy compositions chromium and iron can not diffuse out and be diffused in upper layer from the base mateiral of metal sheet.Alloy compositions chromium and iron are capped because diffusion impervious layer remains in metal sheet and/or thus, have therefore prevented from forming chromium carbide bridge with the point of contact place of adjacent component in subarea.
In the particularly advantageous embodiment of the present invention, aluminium forms the degree of diffusion impervious layer now to summary table surface layer be distributed in upper layer after exceeding this temperature range in.By upper layer, during soldering processes, on metal sheet, producing protectiveness alumina layer, that is, especially, in the case of not providing the other oxygen from appropriate atmosphere.Real soldering processes (herein technical be equivalent to soldering) occur after temperature is further increased to more than 900 DEG C temperature.
The upper layer applying has prevented that carbon from directly contacting with iron with the elemental chromium of the base mateiral of metal sheet especially.Therefore there is not any undesirable combination between adjacent component surface.Correspondingly, can manufacture emission-control equipment, wherein the joint between assembly only forms at the required point of contact place with braze material on surface.The different coefficients of expansion that therefore, can for example prevent each assembly of emission-control equipment lost efficacy because the different length variations in part causes combination between these assemblies.These can be by having the assembly compensation of moving freely property of part relative to each other.The vibration behavior of the assembly of emission-control equipment can be accurately set in addition.
In the particularly advantageous embodiment of the method, v) carry out afterwards another coating processes in step, wherein apply the off gas treatment layer that is completely covered at least a upper layer in subarea.This off gas treatment layer is used in particular for (only) and processes the waste gas transmitting by emission-control equipment.Therefore the upper layer, applying not (obviously) contributes to the conversion of pollutent in waste gas.
On the other hand, proposed particularly to manufacture by the inventive method and/or have the emission-control equipment of at least one metal sheet of preparing by the inventive method of production diffusion impervious layer.
Emission-control equipment comprises at least one honeycomb and shell, and wherein at least honeycomb or shell are formed by least one metal sheet.Described metal sheet forms by comprising at least base mateiral of iron (Fe), chromium (Cr) and aluminium (Al).Described metal sheet has the upper layer at least one subarea, and described upper layer comprises at least aluminum oxide and the metal that is selected from cobalt (Co) and nickel (Ni).At least, in subarea, off gas treatment layer covers described upper layer completely.In addition, on metal sheet, at least in subarea, form brazed joint at least one brazing area.
Especially, about described in the inventive method, those are applicable to the emission-control equipment of the present invention arriving mentioned herein completely.
In addition, propose to have the motor vehicle of at least one oil engine, waste line and emission-control equipment of the present invention.Especially, emission-control equipment is manufactured by the inventive method or is had at least one by the metal sheet making for the production of the inventive method of diffusion impervious layer.
The formation applying or comprise cobalt/cobalt oxide at least and/or the upper layer of nickel oxide special only for being provided for forming the diffusion impervious layer that formed by aluminum oxide and for suppressing the oxygen of chromium carbide bridge at point of contact place herein.Especially, for example also provide and be formed for by forming oxide compound the catalytic active substance that waste gas is purified.And herein in described emission-control equipment, this realizes by providing (at least partly) to be applied on upper layer and optionally having appropriate catalytic off gas treatment layer active and/or that be equipped with the suitable performance conversion of the waste gas component (, be incorporated to, store).Therefore, even if particularly desirably upper layer does not also contact with waste gas during use.In the time that upper layer (only) is between the base mateiral of assembly and off gas treatment layer and/or between the base mateiral of adjacent component and/or between base mateiral and braze material, can avoid by 2 layers of coating (upper layer/diffusion impervious layer and off gas treatment layer) with this contact especially of waste gas.
In particularly advantageous embodiment, off gas treatment layer guarantees that at least cobalt and/or the nickel in upper layer is (substantially) inertia to waste gas.In other words, this to mean element cobalt in upper layer for example and nickel and/or cobalt compound and nickel compound (for example cobalt/nickel oxide) be not catalytic activity to waste gas when for emission-control equipment.Element cobalt and nickel herein (substantially) only for the chromium carbide bridge between the adjacent component of avoiding contacting with each other and for being provided for forming the oxygen of diffusion impervious layer.Therefore, off gas treatment layer (going back) has such function: cobalt and nickel and cobalt compound and nickel compound are reduced to waste gas is transformed and has the degree that can promote with ignoring or not occur at the most this promotion any catalytic activity of waste gas component.
Especially, the in the situation that of other off gas treatment layer, can not (for example, due to diffusion technique) guarantee the complete covering surfaces layer of off gas treatment layer between the usage period of emission-control equipment in case waste gas and the catalytic activity of cobalt and nickel or cobalt compound and nickel compound absolutely not occurs.But, when off gas treatment layer (substantially only) carry out the catalysis of emission-control equipment and upper layer correspondingly (substantially only) when avoiding chromium carbide bridge and be provided for forming the oxygen of diffusion impervious layer, the present invention also can comprise these other off gas treatment layers.
Particularly advantageously completely covering surfaces layer of off gas treatment layer (substantially), and be that enough airtight so that upper layer does not contact with waste gas between the usage period of emission-control equipment.Herein, the component that " airtight " means waste gas especially can not see through coating in upper layer, therefore there is not upper layer, particularly there is (obvious degree) catalyzed reaction between upper layer and the waste gas component of cobalt and nickel and cobalt compound and nickel compound.
In another favourable embodiment, the off gas treatment layer of emission-control equipment comprises at least washcoated layer of one deck (washcoat).Washcoated layer comprises at least one refractory oxide carrier, for example activated alumina (Al conventionally
2o
3), and one or more platinum-group metal component, for example platinum, palladium, rhodium, ruthenium and/or iridium.Conventionally add other additive, for example promotor and washcoated layer stablizer.Washcoated layer provides especially for the king-sized contact area of waste gas.This washcoated layer only after assembling forms emission-control equipment,, after the soldering processes by vacuum or shielding gas condition form brazed joint, is applied on emission-control equipment as off gas treatment layer (at least partly) especially.
Now to be pointed out that again, can be applicable in each case other theme combination with one another about the content described in the each theme of the present invention.
Prepare the work embodiment of diffusion impervious layer:
step a)
The material of base mateiral: material 1.4725
The plate thickness of metal sheet: 50 μ m[microns]
step b)
Metal oxide materials: cobalt/cobalt oxide
The thickness of upper layer: 0.5 μ m
Method of application: PVD method
step c)
Heat treated type/environment: argon shield gas
Heat treated temperature distribution: be heated to 800 DEG C and keep 1.5 hours
The heat treated time length: amount to 3 hours
result:
The extension of diffusion impervious layer: 0.1-1 μ m
Set forth the present invention and corresponding technical field by accompanying drawing below.Accompanying drawing shows particularly preferred embodiment, but, the invention is not restricted to these.Accompanying drawing schematically shows:
Fig. 1: the motor vehicle with emission-control equipment;
Fig. 2: according to processing step metal sheet a) or i);
Fig. 3: according to processing step b) or ii) metal sheet;
Fig. 4: according to processing step metal sheet c) or v);
Fig. 5: according to processing step iii) emission-control equipment;
Fig. 6: according to processing step iv) emission-control equipment;
Fig. 7: according to processing step emission-control equipment v); With
Fig. 8: according to processing step emission-control equipment section v).
Fig. 1 shows the motor vehicle 18 of the emission-control equipment 12 in the waste line 20 that has oil engine 19 and be arranged in oil engine 19.
Fig. 2 shows according to processing step metal sheet 2 a) or i).Metal sheet 2 has surface 6 and is made up of base mateiral 3.In addition the section A that, this figure shows is described in Fig. 3.
Fig. 3 shows processing step b) or ii) later metal sheet 2.Metal sheet 2 is made up of base mateiral 3 and has a upper layer 7 in subarea 5.Upper layer 7 is positioned on the surface 6 of metal sheet 2.Upper layer 7 comprises metal oxide 4.
Fig. 4 shows after processing step c) or v) later metal sheet 2 of processing step.Due to the thermal treatment of processing step c) or v), aluminium 10 is diffused into upper layer 7 from base mateiral 3.Near surface 6 in upper layer 7 regions by the oxygen of metal oxide 4 in the subarea 5 of metal sheet 2, form aluminum oxide 8.Metal oxide 4 is therefore herein as the carrier that aluminium 10 is changed into the required oxygen of aluminum oxide 8.Upper layer 7 has thickness 11.In upper layer 7, due to the heat-treat condition effect of (temperature, time), form the diffusion impervious layer 1 being extended by surface 6 directions to upper layer 7.This diffusion impervious layer 1 is formed by aluminum oxide 8.Aluminium 10 changes into aluminum oxide 8 by the oxygen of metal oxide 4 and causes this metal oxide 4 to change into metal element 9.Correspondingly, at least partly in the time, form multilayered structure herein, it is made up of base mateiral 3, diffusion impervious layer 1 (having the ratio of the metal element 9 of raising) and a part of upper layer 7 with metal oxide 4 ratios of raising, because can not be immediately for forming diffusion impervious layer 1 at upper layer 7 from the aluminium 10 of base mateiral 3.
Fig. 5 shows according to step I ii) emission-control equipment 12, wherein produce herein honeycomb 13 and honeycomb 13 inserted in shell 14.Metal sheet 2 is arranged in honeycomb 13.Honeycomb 13 produces the structure of the emission-control equipment 12 in the waste line 20 that waste gas can flow through and can be used as motor vehicle 18.
Fig. 6 shows according to the step I of the method emission-control equipment 12 v).Herein, braze material 21 is placed in the brazing area 15 of honeycomb 13 and shell 14.Braze material 21 is at least positioned on metal sheet 2.
Fig. 7 shows according to processing step emission-control equipment v).Honeycomb 13 and shell 14 are placed in equipment for Heating Processing 22 to carry out soldering processes.Metal sheet 2 forms honeycomb 13 at least in part.Due to soldering processes, at least in brazing area 15, form brazed joint 16.
Fig. 8 is presented at v) later emission-control equipment 12 of processing step.Metal sheet 2 is upper layer 7 in subarea 5 at least, and it has thickness 11.Upper layer 7 is covered by off gas treatment layer 17 at least in part.In the region of point of contact 23, upper layer 7 is arrange the mode that does not form diffusion joint between another assembly 24 of metal sheet 2 and emission-control equipment 12.Upper layer 7 also forms at brazed joint 16 places.After carrying out soldering processes, between metal sheet 2 and assembly 24, form brazed joint 16 by braze material 21.
Reference numerals list
1 diffusion impervious layer
2 metal sheets
3 base mateirals
4 metal oxides
5 subareas
6 surfaces
7 upper layers
8 aluminum oxide
9 metals
10 aluminium
11 thickness
12 emission-control equipments
13 honeycombs
14 shells
15 brazing areas
16 brazed joints
17 off gas treatment layers
18 motor vehicles
19 oil engines
20 waste lines
21 braze materials
22 equipment for Heating Processing
23 point of contact
24 assemblies
Claims (12)
1. the method for the diffusion impervious layer (1) that comprises aluminum oxide (8) in the upper preparation of metal sheet (2), described metal sheet (2) forms by containing at least base mateiral (3) of iron (Fe), chromium (Cr) and aluminium (Al), and wherein the method comprises at least following steps:
A) provide metal sheet (2),
B) it is upper as upper layer (7) that the starting compound that at least one is selected to the metal oxide (4) of cobalt/cobalt oxide and nickel oxide or at least one can be formed at least one metal oxide that is selected from cobalt/cobalt oxide and nickel oxide (4) because temperature improves is applied at least one subareas (5) on surface (6) of metal sheet (2)
C) on the metal sheet (2) with upper layer (7), carry out more than 650 DEG C thermal treatment and make only at least one subarea (5) of upper layer (7), to form the diffusion impervious layer (1) that comprises aluminum oxide (8), wherein metal oxide (4) is reduced into metal (9) and the aluminium (10) that diffuses out from base mateiral (3) is oxidized to aluminum oxide (8).
According to the process of claim 1 wherein step b) in, metal oxide (4) or starting compound in upper layer (7) exist with the ratio of at least 40 % by weight.
3. according to the method for any one in aforementioned claim, wherein carry out step c) after, aluminum oxide (8) is evenly distributed in upper layer (7).
4. according to the method for any one in aforementioned claim, wherein carry out step c) after, the ratio that is present in the metal (9) of metal oxide (4) in upper layer (7) or starting compound with element form improves at least 5 % by weight.
5. according to the method for any one in aforementioned claim, wherein step a) in aluminium (10) ratio in base mateiral (3) be 1-7 % by weight, step b) in aluminium (10) ratio in metal oxide (4) or starting compound for being no more than 2 % by weight.
6. according to the method for claim 5, wherein carry out step c) after, aluminium (10) ratio in diffusion impervious layer (1) is at least 15 % by weight.
7. according to the method for any one in aforementioned claim, wherein carry out step b) after, upper layer (7) have be no more than 1 μ m[micron] thickness (11).
8. according to the method for any one in aforementioned claim, wherein the base mateiral (3) of step in a) has maximum 20% step metal oxide (4) b) or the metal (9) of starting compound.
9. manufacture the method for emission-control equipment (12), wherein emission-control equipment (12) comprises honeycomb (13) and shell (14), and at least honeycomb (13) or shell (14) are formed by metal sheet (2), and metal sheet (2) forms by comprising at least base mateiral (3) of iron (Fe), chromium (Cr) and aluminium (Al), and wherein the method further comprises at least following steps:
I) provide at least one metal sheet (2) to form shell (14) or honeycomb (13),
Ii) it is upper as upper layer (7) that the starting compound that at least one is selected to the metal oxide (4) of cobalt/cobalt oxide and nickel oxide or at least one can be formed at least one metal oxide that is selected from cobalt/cobalt oxide and nickel oxide (4) because temperature improves is applied at least one subarea (5) on surface (6) of described at least one metal sheet (2)
Iii) form honeycomb (13) and honeycomb (13) inserted in shell (14),
Iv) braze material is put at least in honeycomb (13) or at least one brazing area of shell (14) (15),
V) more than 1000 DEG C, under vacuum or shielding gas, comprising on described at least one metal sheet (2) of metal oxide (4) and carrying out soldering processes, making:
-only at least one subarea (5) in upper layer (7), form the diffusion impervious layer (1) that comprises aluminum oxide (8), wherein metal oxide (4) is reduced into metal (9), the aluminium (10) diffusing out from base mateiral (3) is oxidized to aluminum oxide (8), and
-at the upper brazed joint (16) that forms in described at least one brazing area (15) of described at least one metal sheet (2).
10. according to the method for claim 7, wherein step v) after, carry out further coating processes, apply off gas treatment layer (17) by this technique, it covers the upper layer (7) in described at least one subarea (5) completely.
11. emission-control equipments (12) that comprise honeycomb (13) and shell (14), wherein at least honeycomb (13) or shell (14) are formed by metal sheet (2), and metal sheet (2) is by comprising at least iron (Fe), base mateiral (3) composition of chromium (Cr) and aluminium (Al), and metal sheet (2) has upper layer (7), described upper layer (7) at least comprises at least aluminum oxide (8) and is selected from cobalt (Co) and the metal (9) of nickel (Ni) in subarea (5), wherein off gas treatment layer (17) is completely covered at least the upper layer (7) in subarea (5), in addition, on metal sheet (2), at least in subarea (5), form brazed joint (16) at least one brazing area (15).
12. motor vehicles (18), it has at least one oil engine (19), waste line (20) and according to the emission-control equipment of claim 11 (12).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011119740.4 | 2011-11-30 | ||
| DE102011119740A DE102011119740A1 (en) | 2011-11-30 | 2011-11-30 | Diffusion barrier layer in an exhaust gas treatment unit |
| PCT/EP2012/073634 WO2013079448A2 (en) | 2011-11-30 | 2012-11-26 | Diffusion blocking layer in an exhaust treatment unit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103975090A true CN103975090A (en) | 2014-08-06 |
| CN103975090B CN103975090B (en) | 2016-08-24 |
Family
ID=47222121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280059088.3A Active CN103975090B (en) | 2011-11-30 | 2012-11-26 | Diffusion impervious layer in emission-control equipment |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US9433897B2 (en) |
| EP (1) | EP2785891B1 (en) |
| JP (1) | JP6082020B2 (en) |
| KR (1) | KR101615841B1 (en) |
| CN (1) | CN103975090B (en) |
| DE (1) | DE102011119740A1 (en) |
| RU (1) | RU2596561C2 (en) |
| WO (1) | WO2013079448A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105507992A (en) * | 2015-12-31 | 2016-04-20 | 芜湖恒耀汽车零部件有限公司 | Automobile vent pipe purifier |
| CN113085274A (en) * | 2021-05-07 | 2021-07-09 | 河北德科斯汽车零部件有限公司 | Corrugated composite filter paper with honeycomb filter element and novel sealing method for air outlet end of corrugated composite filter paper |
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|---|---|---|---|---|
| DE102014110534A1 (en) * | 2014-07-25 | 2016-01-28 | Continental Automotive Gmbh | A method of forming a diffusion barrier on a metal sheet and an exhaust treatment unit |
| JP6907876B2 (en) * | 2017-10-19 | 2021-07-21 | 株式会社村田製作所 | Film formation method |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE102011119740A1 (en) | 2013-06-06 |
| US20140260219A1 (en) | 2014-09-18 |
| KR20140106633A (en) | 2014-09-03 |
| EP2785891B1 (en) | 2020-04-15 |
| KR101615841B1 (en) | 2016-04-26 |
| RU2596561C2 (en) | 2016-09-10 |
| WO2013079448A3 (en) | 2014-04-03 |
| US9433897B2 (en) | 2016-09-06 |
| EP2785891A2 (en) | 2014-10-08 |
| JP6082020B2 (en) | 2017-02-15 |
| WO2013079448A2 (en) | 2013-06-06 |
| RU2014126218A (en) | 2016-01-27 |
| CN103975090B (en) | 2016-08-24 |
| JP2015509135A (en) | 2015-03-26 |
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